Novel All‐Nitrogen Molecular Crystals of Aromatic N₁₀

Abstract

Nitrogen has unique bonding ability to form single, double, and triple bonds, similar to that of carbon. However, a molecular crystal formed by an aromatic polynitrogen similar to a carbon system has not been found yet. Herein, a new form of stable all-nitrogen molecular crystals consisting of only bispentazole N₁₀ molecules with exceedingly high energy density is predicted. The crystal structures and the conformation of N₁₀ molecules are strongly correlated, both depending on the applied external pressure. These molecular crystals can be recovered upon the release of the pressure. The first-principles molecular dynamics simulations reveal that these all-nitrogen materials decompose at temperatures much higher than room temperature. The decompositions always start from breaking off N₂ molecules from the nitrogen ring and can release a large amount of energy. These new polynitrogens are aromatic and are more stable than all the other polynitrogen crystals reported previously, providing a new green strategy to get all-nitrogen, nonpolluting high energy density materials without introducing any metal or other guest stabilizer.